Anti-reflective film

ABSTRACT

Disclosed herein is an anti-reflective film comprising: a hard coating layer; and a low-refractive layer containing a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles which are dispersed in the binder resin, wherein a ratio of an average particle diameter of the solid inorganic nanoparticles to an average particle diameter of the hollow inorganic nanoparticles is 0.26 to 0.55, and wherein at least 70 vol % of the entire solid inorganic nanoparticles are present within a distance corresponding to 50% of an entire thickness of the low-refractive layer from the interface between the hard coating layer and the low-refractive layer, and an anti-reflective film comprising: a hard coating layer containing a binder resin containing a photocurable resin, and organic or inorganic fine particles dispersed in the binder resin; and a low-refractive layer containing a binder resin and hollow inorganic nanoparticles and solid inorganic nanoparticles which are dispersed in the binder resin, wherein a ratio of an average particle diameter of the solid inorganic nanoparticles to an average particle diameter of the hollow inorganic nanoparticles is 0.15 to 0.55, and wherein at least 70 vol % of the entire solid inorganic nanoparticles are present within a distance corresponding to 50% of an entire thickness of the low-refractive layer from the interface between the hard coating layer and the low-refractive layer.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Continuation Bypass of International ApplicationNo. PCT/KR2017/007245, filed Jul. 6, 2017, and claims the benefit ofKorean Application No. 10-2016-0089377, filed on Jul. 14, 2016, andKorean Application No. 10-2017-0051842, filed on Apr. 21, 2017, all ofwhich are hereby incorporated by reference in their entirety for allpurposes as if fully set forth herein.

FIELD OF THE INVENTION

The present invention relates to an anti-reflective film. Moreparticularly, the present invention relates to an anti-reflective filmcapable of having a low reflectance and a high light transmittance,simultaneously implementing high scratch-resistance and anti-pollutionproperty, and enhancing sharpness of a screen of a display device.

BACKGROUND OF THE INVENTION

In general, an anti-reflective film is mounted on a flat-panel displaydevice such as a plasma display panel (PDP), a liquid crystal display(LCD), and the like, in order to minimize reflection of light incidentfrom the outside.

As a method for minimizing reflection of light, there are a method ofdispersing fillers such as inorganic fine particles in a resin andcoating the resin on a substrate film to impart unevenness (i.e.anti-glare (AG) coating method), a method of forming a plurality oflayering having different refractive indices on a substrate film to uselight interference (i.e. anti-reflection (AR) coating method), or acombination of these methods, and the like.

Among them, in the case of the AG coating method, an absolute amount ofreflected light is equivalent to that in a general hard coating, but itis possible to obtain a low-reflection effect by decreasing an amount oflight entering the eyes using scattering of the light throughunevenness. However, since in the AG coating method, sharpness of ascreen is deteriorated due to an uneven surface, recently, the ARcoating method has been variously studied.

As a film using the AR coating method, a film having a multilayerstructure in which a hard coating layer (high-refractive index layer), alow-reflective coating layer, and the like, are laminated on a substratefilm has been commercialized. However, in the method of forming aplurality of layers as described above, since a process of forming eachof the layers is separately performed, interlayer close adhesion(interfacial adhesion) may be weak, such that scratch resistance may bedeteriorated.

Further, in order to improve scratch resistance of the low-refractivelayer included in the anti-reflective film, a method of adding variousparticles with a nanometer size (for example, silica particles, aluminaparticle, zeolite particles, or the like) was mainly conducted in thepast. However, in the case of using the particles with a nanometer size,it was difficult to increase scratch resistance while decreasing areflectance of the low-refractive layer, and an anti-pollution propertyof a surface of the low-refractive layer was significantly deteriorateddue to the particles with the nanometer size.

Therefore, various studies for decreasing an absolute reflection amountof light incident from the outside and improving an anti-pollutionproperty together with scratch resistance of a surface have beenconducted, but physical properties of an anti-reflective film are notsufficiently improved in spite of these studies.

DETAILED DESCRIPTION OF THE INVENTION Technical Problem

The present invention has been made in an effort to provide ananti-reflective film having advantages of having a low reflectance and ahigh light transmittance, simultaneously implementing high scratchresistance and anti-pollution property, and enhancing sharpness of ascreen of a display device.

Technical Solution

There is provided an anti-reflective film comprising: a hard coatinglayer; and a low-refractive layer containing a binder resin and hollowinorganic nanoparticles and solid inorganic nanoparticles which aredispersed in the binder resin, wherein a ratio of an average particlediameter of the solid inorganic nanoparticles to an average particlediameter of the hollow inorganic nanoparticles is 0.26 to 0.55, andwherein at least 70 vol % of the entire solid inorganic nanoparticlesare present within a distance corresponding to 50% of an entirethickness of the low-refractive layer from the interface between thehard coating layer and the low-refractive layer.

There also is provided an anti-reflective film comprising: a hardcoating layer containing a binder resin containing a photocurable resin,and organic or inorganic fine particles dispersed in the binder resin;and a low-refractive layer containing a binder resin and hollowinorganic nanoparticles and solid inorganic nanoparticles which aredispersed in the binder resin, wherein a ratio of an average particlediameter of the solid inorganic nanoparticles to an average particlediameter of the hollow inorganic nanoparticles is 0.15 to 0.55, andwherein at least 70 vol % of the entire solid inorganic nanoparticlesare present within a distance corresponding to 50% of an entirethickness of the low-refractive layer from the interface between thehard coating layer and the low-refractive layer.

Hereinafter, the anti-reflective film according to the exemplaryembodiments of the present invention will be described in more detail.

As used herein, the term “photopolymerizable compound” collectivelyrefers to compounds causing a polymerization reaction when light, forexample, visible light or UV light is irradiated thereto.

In addition, the term “fluorine-containing compound” refers to acompound in which at least one fluorine element is contained.

Further, the term “(meth)acryl” is used as a concept including bothacryl and methacryl.

In addition, the term “(co)polymer” is used as a concept including botha co-polymer and a homo-polymer.

Further, the term “hollow silica particles”, which means silicaparticles derived from silicon compounds or organic silicon compounds,means particles in a shape in which an empty space is present onsurfaces and/or the insides of silica particles.

According to the exemplary embodiment of the present invention, there isprovided an anti-reflective film comprising: a hard coating layer; and alow-refractive layer containing a binder resin and hollow inorganicnanoparticles and solid inorganic nanoparticles which are dispersed inthe binder resin, wherein a ratio of an average particle diameter of thesolid inorganic nanoparticles to an average particle diameter of thehollow inorganic nanoparticles is 0.26 to 0.55, and wherein at least 70vol % of the entire solid inorganic nanoparticles are present within adistance corresponding to 50% of an entire thickness of thelow-refractive layer from the interface between the hard coating layerand the low-refractive layer.

The average particle diameters of the hollow particles and the solidparticles may be average values obtained by measuring and calculatingparticle diameters of the hollow particles and the solid particlesconfirmed in a transmission electron microscope (TEM) photograph (forexample, at a magnification of, 25,000×) of the anti-reflective film,respectively.

The present inventors conducted research into an anti-reflective filmand confirmed through experiments that an anti-reflective film includinga low-refractive layer containing hollow particles and solid particleshaving the specific average particle diameter ratio as described abovemay have a lower reflectance and a high light transmittance andsimultaneously implement high scratch resistance and anti-pollutionproperty, thereby completing the present invention.

In a manufacturing process of the low-refractive layer, various factorsaffecting distribution of the hollow particles and the solid particles,for example, manufacturing conditions, weights or densities of theparticles, or the like, may be considered. The present inventorsconfirmed that in the case of adjusting a difference between the averageparticle diameters of the two kinds of particles so as to satisfy theabove-mentioned ratio, in a finally manufactured anti-reflective film, alower reflectance may be secured, and improved scratch resistance andanti-pollution property may be implemented.

In more detail, since the ratio of the average particle diameter of thesolid particles to the average particle diameter of the hollow particlesin the low-refractive layer is 0.55 or less, or 0.15 to 0.55, or 0.26 to0.55, or 0.27 to 0.40, or 0.280 to 0.380, the hollow particles and thesolid particles may be unevenly and differently distributed in thelow-refractive layer. For example, regions of the low-refractive layerin which the hollow particles and the solid particles are mainlydistributed, respectively, may be positioned at different distances froman interface between the hard coating layer and the low-refractivelayer.

As described above, as the regions of the low-refractive layer in whichthe hollow particles and the solid particles are mainly distributed aredifferent from each other, the low-refractive layer may have a uniqueinternal structure and a unique arrangement pattern of components tothereby have a lower reflectance. In addition, as the regions of thelow-refractive layer in which the hollow particles and the solidparticles are mainly distributed are different from each other, surfacecharacteristics of the low-refractive layer are also changed together,thereby making it possible to implement further improved scratchresistance and anti-pollution property.

On the contrary, in the case in which the difference between theparticle diameters of the hollow particles and the solid particlescontained in the low-refractive layer is not very large, the hollowparticles and the solid particles may be aggregated with each other oruneven or different distribution depending on the kind of particles maynot occur, such that it may be difficult to significantly decrease areflectance of the anti-reflective film, and it may also be difficult toachieve the desired scratch resistance and anti-pollution property.

As described above, inherent effects of the anti-reflective filmaccording to the exemplary embodiment, for example, effects of having alow reflectance, simultaneously implementing high light transmittanceand high scratch resistance and anti-pollution property, and enhancingsharpness of a screen of a display device may originate from the ratioof the average particle diameter of the hollow particles and the averageparticle diameter of the solid particles as described above.

The solid inorganic nanoparticles mean particles having a shape in whichan empty space is not present in the insides thereof.

Further, the hollow inorganic nanoparticles mean nanoparticles having ashape in which an empty space is present on surfaces and/or the insidesthereof.

As the ratio of the average particle diameter of the solid particles tothe average particle diameter of the hollow particles as described abovesatisfies a range of 0.55 or less, the anti-reflective film may have alower reflectance and a high light transmittance and simultaneouslyimplement high scratch resistance and anti-pollution property.

In order to more easily adjust characteristics of the anti-reflectivefilm as described above and satisfy characteristics thereof required inan application field, hollow particles and solid particles havingpredetermined average particle diameters, respectively, may be used.

For example, in order to allow the anti-reflective film to have a lowerreflectance and a high light transmittance and implement high scratchresistance and anti-pollution property, the average particle diameter ofhollow particles may be in a range of 40 nm to 100 nm, and the averageparticle diameter of the solid particles may be in a range of 1 nm to 30nm.

When the average particle diameter of the hollow inorganic nanoparticlesand the solid inorganic nanoparticles satisfies the above-mentionedratio or the above-mentioned size range, the range of the specificparticle diameter is not limited to a large extent. However, in order toobtain a more uniform and improved quality of the antireflection film,the particle size of the hollow inorganic nanoparticles may be in therange of 10 nm to 200 nm, or 30 nm to 120 nm, or 38 nm to 80 nm and theparticle size of the solid inorganic nanoparticles may be in the rangeof 0.1 nm to 100 nm, or 0.5 nm to 50 nm, or 2 nm to 25 nm.

The diameter of the solid inorganic nanoparticles and the hollowinorganic nanoparticles may mean the longest diameter of each ofnanoparticles, which is identified on the cross-section.

As long as the average particle diameters of the hollow particles andthe solid particles satisfy the above-mentioned ratio or theabove-mentioned ranges, respectively, specific ranges of the particlediameters thereof are not particularly limited. However, in order toallow the anti-reflective film to have more uniform and improvedquality, the particle diameter of hollow particles may be in a range of10 nm to 200 nm, or 30 nm to 120 nm, and the particle diameter of thesolid particles may also be in a range of 0.1 nm to 100 nm, or 0.5 nm to50 nm.

Meanwhile, each of the solid inorganic nanoparticles and the hollowinorganic nanoparticles may contain one or more reactive functionalgroups selected from the group consisting of a hydroxyl group, a(meth)acrylate group, an epoxide group, a vinyl group, and a thiol groupon a surface thereof. As each of the solid inorganic nanoparticles andthe hollow inorganic nanoparticles contains the above-mentioned reactivefunctional group on the surface thereof, the low-refractive layer mayhave a higher cross-linking density, and thus, it is possible to securefurther improved scratch resistance and anti-pollution property. In thecase which there is no separate substituent, a hydroxyl group may bepresent in the surface of each of the solid inorganic nanoparticles andthe hollow inorganic nanoparticles.

As described above, the anti-reflective film may include the hardcoating layer; and the low-refractive layer containing the binder resin,and hollow inorganic nanoparticles and the solid inorganic nanoparticleswhich are dispersed in the binder resin.

More specifically, in the anti-reflective film, an amount of the solidinorganic nanoparticles distributed closely to the interface between thehard coating layer and the low-refractive layer may be larger than thatof the hollow inorganic nanoparticles.

In the past, in order to increase scratch resistance of ananti-reflective film, an excessive amount of inorganic particles wasadded, but there was a limitation in increasing the scratch resistanceof the anti-reflective film, but the reflectance and the anti-pollutionproperty were rather deteriorated.

On the contrary, in the case in which the hollow inorganic nanoparticlesand the solid inorganic nanoparticles are distributed in thelow-refractive layer included in the anti-reflective film so as to bedistinguished from each other, the anti-reflective film may have a lowreflectance and a high light transmittance and simultaneously implementhigh scratch resistance and anti-pollution property.

More specifically, in the case of mainly distributing the solidinorganic nanoparticles in a region of the low-refractive layer of theanti-reflective film close to the interface between the hard coatinglayer and the low-refractive layer and mainly distributing the hollowinorganic nanoparticles in a region of the low-refractive layer opposeto the interface, it is possible to achieve a reflectance lower than anactual reflectance which could be obtained using the inorganic particlesin the past, and the low-refractive layer may simultaneously implementsignificantly improved scratch resistance and anti-pollution property.

As described above, the low-refractive layer may contain the binderresin and the hollow inorganic nanoparticles and the solid inorganicnanoparticles which are dispersed in the binder resin, and be formed onone surface of the hard coating layer, wherein at least 70 vol % of theentire solid inorganic nanoparticles may be present within a distancecorresponding to 50% of an entire thickness of the low-refractive layerfrom the interface between the hard coating layer and the low-refractivelayer.

‘At least 70 vol % of the entire solid inorganic nanoparticles arepresent in a specific region’, which means that most of the solidinorganic nanoparticles are present in the specific region in a crosssection of the low-refractive layer. In detail, at least 70 vol % of theentire solid inorganic nanoparticles may be confirmed by measuring atotal volume of the solid inorganic nanoparticles or though Transmissionelectron microscope (TEM) or the like.

Whether or not the hollow inorganic nanoparticles and the solidinorganic nanoparticles are present in specific regions may bedetermined by whether each of the hollow inorganic nanoparticles or eachof the solid inorganic nanoparticles is present in the specific region,except for particles present on an interface of the specific region.

Further, as described above, the hollow inorganic nanoparticles may bemainly distributed in the region of the low-refractive layer opposite tothe interface between the hard coating layer and low-refractive layer.In detail, at least 30 vol % of the entire hollow inorganicnanoparticles may be present at a distance farther than that of theentire solid inorganic nanoparticles from the interface between the hardcoating layer and low-refractive layer in a thickness direction of thelow-refractive layer.

In specific, at least 30 vol %, or 50 vol %, or 70 vol % of the entirehollow inorganic nanoparticles may be present in a region of thelow-refractive layer at a distance exceeding 50% of the entire thicknessof the low-refractive layer from the interface between the hard coatinglayer and the low-refractive layer (a region within a point exceeding50% of the total thickness of the low refraction layer from theinterface between the hard coat layer and the low-refractive layer andthe other surface of the low refraction layer facing the interface).

In more detail, at least 70 vol % of the entire solid inorganicnanoparticles may be present within a distance corresponding to 30% ofthe entire thickness of the low-refractive layer from the interfacebetween the hard coating layer and the low-refractive layer. Inaddition, at least 70 vol % of the entire hollow inorganic nanoparticlesmay be present in a region of the low-refractive layer at a distanceexceeding 30% of the entire thickness of the low-refractive layer fromthe interface between the hard coating layer and the low-refractivelayer.

As the solid inorganic nanoparticles are mainly distributed in theregion of the low-refractive layer of the anti-reflective film close tothe interface between the hard coating layer and the low-refractivelayer and the hollow inorganic nanoparticles are mainly distributed inthe region of the low-refractive layer oppose to the interface, two ormore portions or two or more layers having different refractive indicesmay be formed in the low-refractive layer, and thus, the reflectance ofthe anti-reflective film may be decreased.

Specific distribution of the solid inorganic nanoparticles and thehollow inorganic nanoparticles in the low-refractive layer may beobtained by adjusting the ratio of the average particle diameters of thesolid inorganic nanoparticles and the hollow inorganic nanoparticles andadjusting a drying temperature of a photocurable resin composition forforming a low-refractive layer, containing the two kinds ofnanoparticles as described above in a specific manufacturing method tobe described below.

In the case of mainly distributing the solid inorganic nanoparticles inthe region of the low-refractive layer of the anti-reflective film closeto the interface between the hard coating layer and the low-refractivelayer and mainly distributing the hollow inorganic nanoparticles in theregion of the low-refractive layer oppose to the interface, it ispossible to implement a reflectance lower than a reflectance capable ofbeing obtained using inorganic particles in the past. In detail, theanti-reflective film may have average reflectance of 1.5% or less, 1.0%or less, 0.50% to 1.0%, 0.60% to 0.70%, or 0.62% to 0.67% in a visiblelight wavelength region of 380 nm to 780 nm.

Meanwhile, in the anti-reflective film according to the exemplaryembodiment, the low-refractive layer may include a first layercontaining at least 70 vol % of the entire solid inorganic nanoparticlesand a second layer containing at least 70 vol % of the entire hollowinorganic nanoparticles, wherein the first layer may be positioned to becloser to the interface between the hard coating layer and thelow-refractive layer than the second layer.

As described above, the solid inorganic nanoparticles are mainlydistributed in the region of the low-refractive layer of theanti-reflective film close to the interface between the hard coatinglayer and the low-refractive layer, and the hollow inorganicnanoparticles are mainly distributed in the region of the low-refractivelayer opposite to the interface, wherein the regions in which the solidinorganic nanoparticles and the hollow inorganic nanoparticles aremainly distributed, respectively, may form independent layers which maybe visibly confirmed in the low-refractive layer.

In addition, the first layer containing at least 70 vol % of the entiresolid inorganic nanoparticles may be located within 50% of the totalthickness of the low-refractive layer from the interface between thehard coating layer and the low-refractive layer.

More specifically, the first layer containing at least 70 vol % of theentire solid inorganic nanoparticles may be located within 30% of thetotal thickness of the low refractive layer from the interface betweenthe hard coating layer and the low-refractive layer.

Further, as described above, the hollow inorganic nanoparticles may bemainly distributed in the region of the low-refractive layer opposite tothe interface between the hard coating layer and low-refractive layer.In detail, at least 30 vol % of the entire hollow inorganicnanoparticles may be present at a distance farther than that of theentire solid inorganic nanoparticles from the interface between the hardcoating layer and low-refractive layer in a thickness direction of thelow-refractive layer. Accordingly, as described above, the first layermay be positioned closer to the interface between the hard coating layerand the low-refractive layer than the second layer.

As described above, it can be visually confirmed that each of the firstlayer and the second layer, in which the solid inorganic nanoparticlesand the hollow inorganic nanoparticles are mainly distributed,respectively, is present in the low-refractive layer.

For example, it can be visually confirmed that each of the first layerand the second layer is present in the low refractive layer by using atransmission electron microscope or a scanning electron microscope.Further, the ratio of the solid inorganic nanoparticles and the hollowinorganic nanoparticles distributed in the first layer and the secondlayer in the low-refractive layer can also be confirmed.

Meanwhile, each of the first layer containing at least 70 vol % of theentire solid inorganic nanoparticles and the second layer containing atleast 70 vol % of the entire hollow inorganic nanoparticles share acommon optical property in one layer, and thus can be defined as asingle layer.

Specifically, at the time of fitting polarization ellipticity measuredby ellipsometry for the first layer and the second layer included in thelow-refractive layer using a Cauchy model represented by the aboveGeneral Equation 1, they have specific Cauchy parameters A, B, and C sothat the first and second layers can be distinguished from each other.

Also, since the thicknesses of the first layer and the second layer canbe derived through fitting the ellipticity of the polarization measuredby the ellipsometry with a Cauchy model represented by the above GeneralEquation 1, the first layer and the second layer in the low refractivelayer can be defined.

$\begin{matrix}{{n(\lambda)} = {A + \frac{B}{\lambda^{2}} + \frac{C}{\lambda^{4}}}} & \left\lbrack {{General}\mspace{14mu}{Equation}\mspace{14mu} 1} \right\rbrack\end{matrix}$

In General Equation 1, n(λ) is a refractive index at a wavelength of λ,λ is in a range of 300 nm to 1800 nm, and A, B, and C are Cauchyparameters.

Meanwhile, at the time of fitting polarization ellipticity measured byellipsometry using a Cauchy model represented by the above GeneralEquation 1, the Cauchy parameters A, B, and C may be an average value inone layer.

Accordingly, when there is an interface between the first layer and thesecond layer, there may be a region where the first layer and the secondlayer overlap with the Cauchy parameters A, B, and C.

However, even in this case, the thickness and the position of the firstlayer and the second layer can be specified along the region satisfyingthe average value of the Cauchy parameters A, B, and C of each of thefirst layer and the second layer.

For example, at the time of fitting the polarization ellipticitymeasured by ellipsometry for the first layer included in thelow-refractive layer using the Cauchy model represented by GeneralEquation 1, the first layer satisfies the following Conditions: A is 1.0to 1.65, B is 0.0010 to 0.0350, and C is 0 to 1*10⁻³.

In addition, at the time of fitting the polarization ellipticitymeasured by ellipsometry for the first layer included in thelow-refractive layer using the Cauchy model represented by GeneralEquation 1, the first layer satisfies the following conditions: A is1.30 to 1.55, 1.40 to 1.52, or 1.491 to 1.511, B is 0 to 0.005, 0 to0.00580, or 0 to 0.00573, and C is 0 to 1*10⁻³, 0 to 5.0*10⁻⁴, or 0 to4.1352*10⁻⁴.

In detail, at the time of fitting the polarization ellipticity measuredby ellipsometry for the second layer included in the low-refractivelayer using the Cauchy model represented by the following GeneralEquation 1, the second layer may satisfy the following conditions: A is1.0 to 1.50, B is 0 to 0.007, and C is 0 to 1*10⁻³. In addition, at thetime of fitting the polarization ellipticity measured by ellipsometryfor the second layer included in the low-refractive layer using theCauchy model represented by the following General Equation 1, the secondlayer may satisfy the following conditions: A is 1.10 to 1.40, 1.20 to1.35, or 1.211 to 1.349, B is 0 to 0.007, 0 to 0.00550, or 0 to 0.00513,and C is 0 to 1*10⁻³, 0 to 5.0*10⁻⁴, or 0 to 4.8685*10⁻⁴.

In the antireflection film of the embodiment(s) described above, thefirst layer and the second layer included in the low refractive layermay have refractive indexes in different ranges.

More specifically, the first layer included in the low refraction layermay have a refractive index in a range of 1.420 to 1.600, 1.450 to1.550, 1.480 to 1.520, or 1.491 to 1.511, at 550 nm.

In addition, the second layer included in the low refractive layer mayhave a refractive index in a range of 1.200 to 1.410, 1.210 to 1.400, or1.211 to 1.375, at 550 nm.

The refractive index can be measured by a conventionally known method.For example, the refractive index can be determined by calculating therefractive index at 550 nm based on the elliptically polarized light andthe Cauchy model measured at a wavelength of 380 nm to 1000 nm for eachof the first layer and the second layer included in the low refractivelayer

Meanwhile, the low-refractive layer as described above may bemanufactured from a photocurable coating composition containing aphotopolymerizable compound, a fluorine-containing compound including aphotoreactive functional group, the hollow inorganic nanoparticles, thesolid inorganic nanoparticles, and a photoinitiator.

Therefore, the binder resin contained in the low-refractive layer maycontain a cross-linked (co)polymer between a (co)polymer of thephotopolymerizable compound and the fluorine-containing compoundincluding the photoreactive functional group.

The photopolymerizable compound contained in the photocurable coatingcomposition according to the exemplary embodiment may form a substrateof the binder resin of the manufactured low-refractive layer. In detail,the photopolymerizable compound may include a monomer or oligomerincluding (meth)acrylate or a vinyl group. In more detail, thephotopolymerizable compound may include a monomer or oligomer, includingat least one, at least two, or at least three (meth)acrylates or vinylgroups.

A specific example of the monomer or oligomer including (meth)acrylatemay include pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, tripentaerythritolhepta(meth)acrylate, trilene diisocyanate, xylene diisocyanate,hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate,trimethylolpropane polyethoxy tri(meth)acrylate, trimethylolpropanetrimethacrylate, ethyleneglycol dimethacrylate, butanedioldimethacrylate, hexaethyl methacrylate, butyl methacrylate, or a mixtureof two or more thereof; or an urethane modified acrylate oligomer, anepoxide acrylate oligomer, an etheracrylate oligomer, a dendriticacrylate oligomer, or a mixture of two or more thereof. Here, it ispreferable that a molecular weigh of the oligomer is 1,000 to 10,000.

A specific example of the monomer or oligomer including the vinyl groupmay include divinyl benzene, styrene, or paramethylstyrene.

A content of the photopolymerizable compound in the photocurable coatingcomposition is not particularly limited, but in consideration ofmechanical properties, and the like, of a low-refractive layer oranti-reflective film to be finally manufactured, the content of thephotopolymerizable compound may be 5 wt % to 80 wt % based on a solidcomponent of the photocurable coating composition. The solid componentof the photocurable coating composition means only a solid-statecomponent of the photocurable coating composition except forliquid-state components, for example, an organic solvent, and the like,which may be selectively contained as described below.

Meanwhile, the photopolymerizable compound may further contain afluorinated (meth)acrylate based monomer or oligomer in addition to theabove-mentioned monomer or oligomer. In the case in which thephotopolymerizable compound further contains the fluorinated(meth)acrylate based monomer or oligomer, a weight ratio of thefluorinated (meth)acrylate based monomer or oligomer to the monomer oroligomer including the (meth)acrylate or vinyl group may be 0.1% to 10%.

A specific example of the fluorinated (meth)acrylate based monomer oroligomer may include one or more selected from the group consisting ofcompounds represented by the following Chemical Formulas 1 to 5.

In Chemical Formula 1, R1 is hydrogen or an alkyl group having 1 to 6carbon atoms, a is an integer of 0 to 7, and b is an integer of 1 to 3.

In Chemical Formula 2, c is an integer of 1 to 10.

In Chemical Formula 3, d is an integer of 1 to 11.

In Chemical Formula 4, e is an integer of 1 to 5.

In Chemical Formula 5, F is an integer of 4 to 10.

Meanwhile, a moiety derived from the fluorine-containing compoundincluding the photoreactive functional group may be contained in thelow-refractive layer.

One or more photoreactive functional groups may be included orsubstituted in the fluorine-containing compound including thephotoreactive functional group, wherein the photoreactive functionalgroup means a functional group capable of participating in apolymerization reaction by light irradiation, for example, visible lightirradiation or UV light irradiation. The photoreactive functional groupmay include various functional groups known to participate in apolymerization reaction by light irradiation, and a specific examplethereof may include a (meth)acrylate group, an epoxide group, a vinylgroup, or a thiol group.

Each of the fluorine-containing compounds including the photoreactivefunctional group may have a weight average molecular weight (weightaverage molecular weight measured by gel permeation chromatography (GPC)in terms of polystyrene) of 2,000 to 200,000, preferably 5,000 to100,000.

When the weight average molecular weight of the fluorine-containingcompounds including the photoreactive functional group is excessivelysmall, the fluorine-containing compounds in the photocurable coatingcomposition may not be uniformly and effectively arranged on a surfacebut are positioned inside the finally manufactured low-refractive layer,such that the anti-pollution property of the surface of thelow-refractive layer may be deteriorated, and mechanical properties suchas entire strength, scratch resistance, and the like, may bedeteriorated due to a decrease in the cross-linking density of thelow-refractive layer.

Further, when the weight average molecular weight of thefluorine-containing compounds including the photoreactive functionalgroup is excessively large, compatibility with other components in thephotocurable coating composition may be deteriorated, such that a hazeof the finally manufactured low-refractive layer may be increased orlight transmittance thereof may be decreased, and strength of thelow-refractive layer may also be deteriorated.

In detail, the fluorine-containing compound including the photoreactivefunctional group may be i) an aliphatic compound or alicyclic compoundin which one or more photoreactive functional groups are substituted,and at least one carbon atom is substituted with one or more fluorineatoms; ii) a hetero aliphatic compound or hetero alicyclic compound inwhich one or more photoreactive functional groups are substituted, atleast one hydrogen atom is substituted with a fluorine atom, and one ormore carbon atoms are substituted with a silicon atom; iii) apolydialkylsiloxane based polymer (for example, polydimethylsiloxanebased polymer) in which one or more photoreactive functional groups aresubstituted, and at least one silicon atom is substituted with one ormore fluorine atoms; iv) a polyether compound in which one or morephotoreactive functional groups are substituted, and at least onehydrogen atom is substituted with a fluorine atom; or a mixture of twoor more of i) to iv) or a copolymer thereof.

The photocurable coating composition may contain 20 to 300 parts byweight of the fluorine-containing compound including the photoreactivefunctional group, based on 100 parts by weight of the photopolymerizablecompound.

When an amount of the fluorine-containing compound including thephotoreactive functional group is excessively large as compared to thephotopolymerizable compound, a coating property of the photocurablecoating composition according to the exemplary embodiment may bedeteriorated, or the low-refractive layer obtained from the photocurablecoating composition may not have sufficient durability or scratchresistance. Further, when the amount of the fluorine-containing compoundincluding the photoreactive functional group is excessively small ascompared to the photopolymerizable compound, the low-refractive layerobtained from the photocurable coating composition may not havesufficient mechanical properties such as the anti-pollution property,scratch resistance, or the like.

The fluorine-containing compound including the photoreactive functionalgroup may further contain silicon or a silicon compound. That is, thefluorine-containing compound including the photoreactive functionalgroup may selectively contain silicon or the silicon compound therein.More specifically, a content of silicon in the fluorine-containingcompound including the photoreactive functional group may be 0.1 wt % to20 wt %.

The silicon contained in the fluorine-containing compound including thephotoreactive functional group may improve compatibility with othercomponents contained in the photocurable coating composition accordingto the exemplary embodiment, and thus, the silicon may serve to increasetransparency by preventing haze generation in the finally manufacturerefractive layer. Meanwhile, when the content of silicon in thefluorine-containing compound including the photoreactive functionalgroup is excessively high, compatibility between other ingredientscontained in the photocurable coating composition and thefluorine-containing compound may be rather deteriorated, and thus, thefinally manufactured low-refractive layer or anti-reflective film maynot have a sufficient light transmittance or anti-reflectionperformance, such that the anti-pollution property of the surface mayalso be deteriorated.

The low-refractive layer may contain 100 to 400 parts by weight of thehollow inorganic nanoparticles and 10 to 400 parts by weight of thesolid inorganic nanoparticles, based on 100 parts by weigh of the(co)polymer of the photopolymerizable compound.

In the case in which the contents of the hollow inorganic nanoparticlesand the solid inorganic nanoparticles in the low-refractive layer areexcessively high, in a manufacturing process of the low-refractivelayer, the hollow inorganic nanoparticles and the solid inorganicnanoparticles may not be sufficiently phase-separated, but mixedlyexist, such that the reflectance may be increased, and the surface maybecome excessively uneven, such that the anti-pollution property may bedeteriorated. Further, in the case in which the contents of the hollowinorganic nanoparticles and the solid inorganic nanoparticles in thelow-refractive layer are excessively low, it may be difficult to allowthe solid inorganic nanoparticles to be mainly positioned in the regionclose to the interface between the hard coating layer and thelow-refractive layer, and the reflectance of the low-refractive layermay be significantly increased.

The low-refractive layer may have a thickness of 1 nm to 300 nm, or 50nm to 200 nm, or 85 nm to 300 nm.

Meanwhile, as the hard coating layer, a hard coating layer generallyknown in the art may be used without limitation.

As an example of the hard coating layer, there is a hard coating layercontaining a binder resin containing a photocurable resin, and organicor inorganic fine particles dispersed in the binder resin.

The photocurable resin contained in the hard coating layer, which is apolymer of a photocurable compound capable of causing a polymerizationreaction when light such as UV light, or the like, is irradiated, may bea photocurable resin generally used in the art.

In detail, the photocurable resin may include one or more selected fromthe group consisting of the reactive acrylate oligomer group consistingof an urethane acrylate oligomer, an epoxide acrylate oligomer,polyester acrylate, and polyether acrylate; and the multi-functionalacrylate monomer group consisting of dipentaerythritol hexaacrylate,dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate,pentaerythritol triacrylate, trimethylene propyl triacrylate,propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate,1,6-dihexanediol acrylate, propoxylated glycero triacrylate,tripropylene glycol diacrylate, and ethylene glycol diacrylate.

A particle diameter of the organic or inorganic fine particles is notspecifically limited, but for example, the organic fine particles mayhave a particle diameter of 1 to 10 μm, and the inorganic fine particlesmay have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm.

The particle diameter of the organic or inorganic fine particles may bedefined as a volume average particle diameter.

Specific examples of the organic or inorganic fine particles containedin the hard coating layer are not limited, but may include, for example,organic fine particles made of an acrylic resin, a styrene based resin,an epoxide resin, and a nylon resin, or inorganic fine particles made ofsilicon oxide, titanium dioxide, indium oxide, tin oxide, zirconiumoxide, and zinc oxide.

The binder resin of the hard coating layer further comprises ahigh-molecular weight (co)polymer having weight average molecular weightof 10,000 or more.

The high-molecular weight (co)polymer may be one or more selected fromthe group consisting of a cellulose based polymer, an acrylic polymer, astyrene based polymer, an epoxide based polymer, a nylon based polymer,an urethane based polymer, and a polyolefin based polymer.

Meanwhile, as another example of the hard coating layer, there is a hardcoating layer containing a binder resin made of a photocurable resin;and an antistatic agent dispersed in the binder resin.

The photocurable resin contained in the hard coating layer, which is apolymer of a photocurable compound capable of causing a polymerizationreaction when light such as UV light, or the like, is irradiated, may bea photocurable resin generally used in the art. However, preferably, thephotocurable compound may be a multi-functional (meth)acrylate basedmonomer or oligomer. Here, in view of securing physical properties ofthe hard coating layer, the number of (meth)acrylate based functionalgroups is 2 to 10, preferably, 2 to 8, and more preferably 2 to 7. Morepreferably, the photocurable compound may be one or more selected fromthe group consisting of pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate,dipentaerythritol hepta(meth)acrylate, tripentaerythritolhepta(meth)acrylate, trilene diisocyanate, xylene diisocyanate,hexamethylene diisocyanate, trimethylolpropane tri(meth)acrylate, andtrimethylolpropane polyethoxy tri(meth)acrylate.

The antistatic agent may be a quaternary ammonium salt compound; apyridinium salt; a cationic compound having 1 to 3 amino groups; ananionic compound such as a sulfonic acid base, a sulfuric acid esterbase, a phosphoric acid ester base, a phosphonic acid base, or the like;an amphoteric compound such as an amino acid based or amino sulfuricacid ester based compound, or the like; a non-ionic compound such as animino alcohol based compound, a glycerine bsed compound, a polyethyleneglycol based compound, or the like; an organic metal compound such asmetal alkoxide compound containing tin, titanium, etc., or the like; ametal chelate compound such as an acetylacetonate salt of the organicmetal compound, or the like; a reaction product or polymer compound oftwo or more thereof; or a mixture of two or more thereof. Here, thequaternary ammonium salt compound may be a compound having one or morequaternary ammonium salt groups in a molecule, and a low-molecularweight quaternary ammonium salt compound or a high-molecular weightquaternary ammonium salt compound may be used without limitation.

Further, as the antistatic agent, a conductive polymer and metal oxidefine particles may also be used. An example of the conductive polymerincludes aromatic conjugated poly(paraphenylene), heterocyclicconjugated polypyrrole, polythiophene, aliphatic conjugatedpolyacetylene, hetero atom-containing conjugated polyaniline, and mixedtype conjugated poly(phenylenevinylene), a double chain conjugatedcompound, which is conjugated compound having a plurality of conjugatedchains in a molecule, a conductive complex in which a conjugated polymerchain is grafted to or block-copolymerized with a saturated polymer, andthe like. Further, the metal oxide fine particles may be made of zincoxide, antimony oxide, tin oxide, cerium oxide, indium tin oxide, indiumoxide, aluminum oxide, tin oxide doped with antimony, zinc oxide dopedwith aluminum, or the like.

The hard coating film containing the binder resin made of thephotocurable resin; and the antistatic agent dispersed in the binderresin may further contain one or more compounds selected from the groupconsisting of an alkoxy silane based oligomer and a metal alkoxide basedoligomer.

The alkoxy silane based compound may be is an alkoxy silane basedcompound generally used in the art, but may be preferably one or morecompounds selected from the group consisting of tetramethoxysilane,tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane,methyltriethoxysilane, methacryloxylpropyltrimethoxysilane,glycidoxypropyl trimethoxysilane, and glycidoxypropyl triethoxysilane.

Further, the metal alkoxide based oligomer may be prepared by a sol-gelreaction of a composition containing a metal alkoxide based compound andwater. The sol-gel reaction may be carried out by a method equivalent toa preparation method of the alkoxy silane based oligomer describedabove.

However, since the metal alkoxide based compound may violently reactwith water, the sol-gel reaction may be carried out by diluting themetal alkoxide based compound in an organic solvent and then slowlydropping water thereinto. Here, it is preferable that a molar ratio(based on a metal ion) of the metal alkoxide compound to water isadjusted in a range of 3 to 170 in consideration of reaction efficiency,or the like.

Here, the metal alkoxide based compound may be one or more compoundsselected from the group consisting of titanium tetra-isopropoxide,zirconium isopropoxide, and aluminum isopropoxide.

As another example of the hard coating film, there is an antiglare filmhaving a surface on which an uneven shape is formed, or a film having asurface subjected to antiglare treatment (haze imparting treatment, orthe like).

As an example of the hard coating film, there is a hard coating filmcontaining a binder resin containing a photocurable resin and organic orinorganic fine particles dispersed in the binder resin.

The photocurable resin contained in the hard coating layer, which is apolymer of a photocurable compound capable of causing a polymerizationreaction when light such as UV light, or the like, is irradiated, may bea photocurable resin generally used in the art.

The organic or inorganic fine particles may have a particle diameter of1 to 10 μm.

The organic or inorganic fine particles may be organic fine particlesmade of an acrylic resin, a styrene based resin, an epoxide resin, and anylon resin, or inorganic fine particles made of silicon oxide, titaniumdioxide, indium oxide, tin oxide, zirconium oxide, and zinc oxide.

Meanwhile, the hard coating layer may have a thickness of 0.1 μm to 100μm.

The anti-reflective film may further include a substrate bonded to theother surface of the hard coating layer. A specific kind or thickness ofsubstrate is not particularly limited, but a substrate known to be usedfor manufacturing a low-refractive layer or anti-reflective film may beused without limitation. For example, as the substrate, a substrate madeof polycarbonate, a cyclo olefin polymer, polyester, triacetylcellulose, or the like, may be used.

Meanwhile, the low-refractive layer may further contain a silane basedcompound including one or more reactive functional groups selected fromthe group consisting of a vinyl group and a (meth)acrylate group.

The silane based compound including one or more reactive functionalgroups selected from the group consisting of the vinyl group and the(meth)acrylate group may improve mechanical properties, for example,scratch resistance, of the low-refractive layer, due to the reactivefunctional group. Further, as the low-refractive layer may furthercontain the silane based compound including one or more reactivefunctional groups selected from the group consisting of a vinyl groupand a (meth)acrylate group, it is possible to secure further improvedscratch resistance.

In addition, due to a silane functional group or a silicon atom includedin the silane based compound including one or more reactive functionalgroups selected from the group consisting of the vinyl group and the(meth)acrylate group, it is possible to improve internal characteristicsof the low-refractive layer. In more detail, as the silane functionalgroup or the silicon atom included in the silane based compound isuniformly distributed in the low-refractive layer, a lower averagereflectance may be implemented, and inorganic fine particles uniformlydistributed in the low-refractive layer may be uniformly bound to thephotopolymerizable compound due to the silane functional group or thesilicon atom, thereby making it possible to improve scratch resistanceof the finally manufactured ant-reflective film.

As described above, as the silane based compound including one or morereactive functional groups selected from the group consisting of thevinyl group and the (meth)acrylate group has a chemical structureincluding both the reactive functional group and the silicon atom, theinternal characteristics of the low-refractive layer may be optimized todecrease the refractive index, and thus, the low-refractive layer mayimplement a low reflectance and a high light transmittance, and secure auniform cross-linking density to secure more excellent abrasionresistance or scratch resistance.

More specifically, the silane based compound including one or morereactive functional groups selected from the group consisting of thevinyl group and the (meth)acrylate group may contain 100 to 1000 g/mol(equivalent weight) of the reactive functional group.

When a content of the reactive functional group in the silane basedcompound including one or more reactive functional groups selected fromthe group consisting of the vinyl group and the (meth)acrylate group isexcessively low, it may be difficult to sufficiently improve scratchresistance or mechanical properties of the low-refractive layer.

Meanwhile, when the content of the reactive functional group in thesilane based compound including one or more reactive functional groupsselected from the group consisting of the vinyl group and the(meth)acrylate group is excessively high, uniformity or dispersibilityof the inorganic fine particles in the low-refractive layer may bedeteriorated, such that the light transmittance, or the like, of thelow-refractive layer may be rather deteriorated.

The silane based compound including one or more reactive functionalgroups selected from the group consisting of the vinyl group and the(meth)acrylate group may have a weight average molecular weight (weightaverage molecular weight measured by gel permeation chromatography (GPC)in terms of polystyrene) of 100 to 5,000, or 200 to 3,000.

In detail, the silane based compound including one or more reactivefunctional groups selected from the group consisting of the vinyl groupand the (meth)acrylate group may include one or more reactive functionalgroups selected from the group consisting of the vinyl group and the(meth)acrylate group, one or more trialkoxysliane groups to which analkylene group having 1 to 10 carbon atoms are bound, and an organicfunctional group including an urethane functional group. Thetrialkoxysilane group may be a functional group in which three alkoxygroups having 1 to 3 carbon atoms are substituted in a silicon compound.

Although a specific chemical structure of the silane based compoundincluding one or more reactive functional groups selected from the groupconsisting of the vinyl group and the (meth)acrylate group is notlimited, a specific example of the silane based compound may includecompounds represented by the following Chemical Formulas 11 to 14, but aspecific chemical structure thereof is not limited.

In Chemical Formula 14, R¹ is

X is any one of hydrogen, a monovalent residue derived from an aliphatichydrocarbon having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, and an alkoxycarbonyl group having 1 to 4 carbon atoms,

Y is a single bond, —CO—, or —COO—,

R² is a divalent residue derived from aliphatic hydrocarbon having 1 to20 carbon atoms, a divalent residue in which one or more hydrogen atomsare substituted with a hydroxyl group, a carboxyl group, or an epoxygroup, or a divalent residue in which one or more —CH₂— groups arereplaced with —O—, —CO—O—, —O—CO—, or —O—CO—O— so that oxygen atoms arenot directly linked to one another, and

A is any one of hydrogen and a monovalent residue derived from aliphatichydrocarbon having 1 to 6 carbon atoms, B is any one of monovalentresidues derived from aliphatic hydrocarbon having 1 to 6 carbon atoms,and n is an integer of 0 to 2.

As an example of the compound represented by Chemical Formula 14, thereis a compound represented by Chemical Formula 15.

In Chemical Formula 15, R₁, R₂, and R₃ are alkoxy groups having 1 to 3carbon atoms or hydrogen, X is a straight or branched chain alkylenegroup having 1 to 10 carbon atoms, and R₄ is an alkyl group having 1 to3 carbon atoms or hydrogen.

The low-refractive layer may contain 2 to 40 parts by weight of thesilane based compound including one or more reactive functional groupsselected from the group consisting of the vinyl group and the(meth)acrylate group, based on 100 parts by weight of thephotopolymerizable compound contained in the low-refractive layer.

When the content of the silane based compound including one or morereactive functional groups selected from the group consisting of a vinylgroup and a (meth)acrylate group based on the photopolymerizablecompound is excessively low, it may be difficult to sufficiently securescratch resistance of the low-refractive layer. Further, when thecontent of the silane based compound including one or more reactivefunctional groups selected from the group consisting of a vinyl groupand a (meth)acrylate group based on the photopolymerizable compound isexcessively high, compatibility with other components contained in thelow-refractive layer may be significantly deteriorated, such that a hazemay occur in the low-refractive layer or the anti-reflective film, ortransparence of the low-refractive layer or the anti-reflective film maybe significantly deteriorated, and scratch resistance may be ratherdeteriorated.

Meanwhile, the anti-reflective film according to the exemplaryembodiment may be manufactured by a manufacturing method of ananti-reflective film including applying a resin composition for forminga low-refractive layer, containing a photocurable compound or a(co)polymer thereof, a fluorine-containing compound including aphotoreactive functional group, a photoinitiator, hollow inorganicnanoparticles, and solid inorganic nanoparticles on a hard coating layerand drying the applied resin composition at a temperature of 35° C. to100° C.; and photocuring the dried resin composition.

More specifically, in the anti-reflective film manufactured by themanufacturing method of an anti-reflective film described above, thehollow inorganic nanoparticles and the solid inorganic nanoparticles aredistributed in the low-refractive layer so as to be distinguished fromeach other, such that the anti-reflective film may have a lowreflectance and a high light transmittance and simultaneously implementhigh scratch resistance and anti-pollution property.

In more detail, the anti-reflective film may include the hard coatinglayer; and the low-refractive layer formed on one surface of the hardcoating layer and containing the binder resin and the hollow inorganicnanoparticles and the solid inorganic nanoparticles which are dispersedin the binder resin, wherein at least 70 vol % of the entire solidinorganic nanoparticles may be present within a distance correspondingto 50% of an entire thickness of the low-refractive layer from aninterface between the hard coating layer and the low-refractive layer.

Further, at least 30 vol % of the entire hollow inorganic nanoparticlesmay be present at a distance farther than that of the entire solidinorganic nanoparticles from the interface between the hard coatinglayer and low-refractive layer in a thickness direction of thelow-refractive layer.

Further, at least 70 vol % of the entire solid inorganic nanoparticlesmay be present within a distance corresponding to 30% of the entirethickness of the low-refractive layer from the interface between thehard coating layer and the low-refractive layer. In addition, at least70 vol % of the entire hollow inorganic nanoparticles may be present ina region of the low-refractive layer at a distance exceeding 30% of thetotal thickness of the low-refractive layer from the interface betweenthe hard coating layer and the low-refractive layer.

Further, in the anti-reflective film manufactured by the manufacturingmethod of an anti-reflective film, the low-refractive layer may includea first layer containing at least 70 vol % of the entire solid inorganicnanoparticles and a second layer containing at least 70 vol % l of theentire hollow inorganic nanoparticles, wherein the first layer may bepositioned to be closer to the interface between the hard coating layerand the low-refractive layer than the second layer.

The low-refractive layer may be formed by applying the resin compositionfor forming a low-refractive layer, containing the photocurable compoundor the (co)polymer thereof, the fluorine-containing compound includingthe photoreactive functional group, the photoinitiator, the hollowinorganic nanoparticles, and the solid inorganic nanoparticles on thehard coating layer and drying the applied resin composition at atemperature of 35° C. to 100° C. or 40° C. to 80° C.

When a drying temperature of the resin composition for forming alow-refractive layer applied on the hard coating layer is lower than 35°C., an anti-pollution property of the formed low-refractive layer may besignificantly deteriorated. Further, when the drying temperature of theresin composition for forming a low-refractive layer applied on the hardcoating layer is higher than 100° C., in a manufacturing process of thelow-refractive layer, the hollow inorganic nanoparticles and the solidinorganic nanoparticles may not be sufficiently phase-separated, butmixedly exist, such that the scratch resistance and anti-pollutionproperty of the low-refractive layer may be deteriorated, and thereflectance may also be significantly increased.

The low-refractive layer having the-above mentioned characteristics maybe formed by adjusting a density difference between the solid inorganicnanoparticles and the hollow inorganic nanoparticles in addition to thedrying temperature during a drying process of the resin composition forforming a low-refractive layer applied on the hard coating layer. Adensity of the solid inorganic nanoparticles may be at least 0.50 g/cm³larger than that of the hollow inorganic nanoparticles, and due to thedensity difference, the solid inorganic nanoparticles may be positionedin the low-refractive layer formed on the hard coating layer to be closeto the hard coating layer.

Meanwhile, the drying of the resin composition for forming alow-refractive layer, applied on the hard coating layer at a temperatureof 35 to 100° C. may be performed for 10 seconds to 5 minutes, or 30seconds to 4 minutes.

When a drying time is excessively short, a phase separation phenomenonbetween the hollow inorganic nanoparticles and the solid inorganicnanoparticles described above may not sufficiently occur. On thecontrary, when the drying time is excessively long, the formedlow-refractive layer may infiltrate into the hard coating layer.

Meanwhile, the low-refractive layer may be manufactured from aphotocurable coating composition containing a photocurable compound or a(co)polymer thereof, a fluorine-containing compound including aphotoreactive functional group, the hollow inorganic nanoparticles, thesolid inorganic nanoparticles, and a photoinitiator.

The low-refractive layer may be obtained by photocuring the resultantobtained by applying the photocurable coating composition on apredetermined substrate. A specific kind or thickness of substrate isnot particularly limited, but a substrate known to be used formanufacturing a low-refractive layer or anti-reflective film may be usedwithout limitation.

A method and an apparatus generally used to apply the photocurablecoating composition may be used without particular limitation. Forexample, a bar coating method such as a Meyer bar coating method, or thelike, a gravure coating method, a 2-roll reverse coating method, avacuum slot die coating method, a 2-roll coating method, or the like,may be used.

The low-refractive layer may have a thickness of 1 nm to 300 nm, or 50nm to 200 nm. Therefore, a thickness of the photocurable coatingcomposition applied on the predetermined substrate may be about 1 nm to300 nm or 50 nm to 200 nm.

In the photocuring of the photocurable coating composition, UV light orvisible light, having a wavelength of 200 to 400 nm, may be irradiated,and at the time of irradiation, it is preferable that an exposure amountis 100 to 4,000 mJ/cm². An exposure time is not particularly limited,but may be suitably changed depending on a used exposure device, awavelength of the irradiated light, or the exposure amount.

Further, in the photocuring of the photocurable coating composition,nitrogen purging, or the like, may be performed in order to apply anitrogen atmosphere condition.

Detailed contents of the photocurable compound, the hollow inorganicnanoparticles, the solid inorganic nanoparticles, and thefluorine-containing compound including the photo-reactive functionalgroup include those in the anti-reflective film according to theexemplary embodiment described above.

Each of the hollow inorganic nanoparticles and the solid inorganicnanoparticles may be contained in the composition as a colloidal phasein which they are dispersed in a predetermined dispersion medium. Thecolloidal phase containing each of the hollow inorganic nanoparticlesand the solid inorganic nanoparticles may contain an organic solvent asthe dispersion medium.

A content of the hollow inorganic nanoparticles and a content of thesolid inorganic nanoparticles in the colloidal phase may be determinedin consideration of a content range of the hollow inorganicnanoparticles and a content range of the solid inorganic nanoparticlesin the photocurable coating composition, a viscosity of the photocurablecoating composition, or the like. For example, solid contents of thehollow inorganic nanoparticles and the solid inorganic nanoparticles inthe colloidal phase may be 5 wt % to 60 wt %, respectively.

Here, an example of the organic solvent used as the dispersion mediummay include alcohols such as methanol, isopropylalcohol, ethyleneglycol,butanol, and the like; ketones such as methylethylketone,methylisobutylketone, and the like; aromatic hydrocarbons such astoluene, xylene, and the like; amides such as dimethylformamide,dimethylacetamide, N-methylpyrrolidone, and the like; esters such asethyl acetate, butyl acetate, gamma-butyrolactone, and the like; etherssuch as tetrahydrofuran, 1,4-dioxane, and the like; or a mixturethereof.

As the photoinitiator, any compound may be used without particularlimitation as long as it is known to be usable in a photocurable resincomposition. More specifically, a benzophenone based compound, anacetophenone based compound, a biimidazole based compound, a triazinebased compound, an oxime based compound, or a mixture of two or morethereof may be used.

The photoinitiator may be used in a content of 1 to 100 parts by weightbased on 100 parts by weight of the photopolymerizable compound. Whenthe content of the photoinitiator is excessively low, some materialsthat are not cured in the photocuring of the photocurable coatingcomposition may remain. When the content of the photoinitiator isexcessively high, an unreacted initiator may remain as an impurity or across-linking density may be decreased, such that mechanical property ofa manufactured film may be deteriorated, or a reflectance thereof may besignificantly increased.

Meanwhile, the photocurable coating composition may further contain anorganic solvent.

A non-restrictive example of the organic solvent may include ketones,alcohols, acetates, and ethers, or a mixture of two or more thereof.

A specific example of the organic solvent as described above may includethe ketones such as methylethylketone, methylisobutylketone,acetylacetone, isobutylketone, or the like; the alcohols such asmethanol, ethanol, diacetone alcohol, n-propanol, i-propanol, n-butanol,i-butanol, t-butanol, or the like; the acetates such as ethylacetate,i-propylacetate, polyethyleneglycol monomethylether acetate, or thelike; the ethers such as tetrahydrofuran, propyleneglycolmonomethylether, or the like; or a mixture of two or more thereof.

The organic solvent may be added at the time of mixing each of thecomponents contained in the photocurable coating composition, or beadded in a state in which each of the components is dispersed in ormixed with the organic solvent, the organic solvent may be contained inthe photocurable coating composition. When a content of the organicsolvent in the photocurable coating composition is excessively low,flowability of the photocurable coating composition may be deteriorated,such that defects such as formation of a stripe pattern, or the like,may occur in the finally manufactured film. Further, when the organicsolvent is excessively added, a solid content may be decreased, suchthat coating and film formation may not be sufficiently performed, andthus physical properties or surface characteristics of the film may bedeteriorated, and a defect may occur in the drying and curing processes.Therefore, the photocurable coating composition may contain the organicsolvent so that a total content of the solid components containedtherein is 1 wt % to 50 wt %, or 2 wt % to 20 wt %.

A material of the hard coating layer is not particularly limited as longas it is known to be usable in an anti-reflective film.

In detail, the manufacturing method of an anti-reflective film mayfurther include applying a polymer resin composition for forming a hardcoating layer, containing a photocurable compound or a (co)polymerthereof, a photoinitiator, and an antistatic agent on a substrate andphotocuring the applied polymer resin composition, and the hard coatinglayer may be formed by this step.

The components used to form the hard coating layer are the same as thosein the anti-reflective film according to the present invention describedabove.

Further, the polymer resin composition for forming a hard coating layermay further contain one or more compounds selected from the groupconsisting of an alkoxy silane based oligomer and a metal alkoxide basedoligomer.

A method and an apparatus generally used to apply the polymer resincomposition for forming a hard coating layer may be used withoutparticular limitation. For example, a bar coating method such as a Meyerbar coating method, or the like, a gravure coating method, a 2-rollreverse coating method, a vacuum slot die coating method, a 2-rollcoating method, or the like, may be used.

In the photocuring of the polymer resin composition for forming a hardcoating layer, UV light or visible light, having a wavelength of 200 to400 nm, may be irradiated, and at the time of irradiation, it ispreferable that an exposure amount is 100 to 4,000 mJ/cm². An exposuretime is not particularly limited, but may be suitably changed dependingon a used exposure device, a wavelength of the irradiated light, or theexposure amount. Further, in the photocuring of the polymer resincomposition for forming a hard coating layer, nitrogen purging, or thelike, may be performed in order to apply a nitrogen atmospherecondition.

Meanwhile, according to the another exemplary embodiment of the presentinvention, there is provided an anti-reflective film comprising: a hardcoating layer containing a binder resin containing a photocurable resin,and organic or inorganic fine particles dispersed in the binder resin;and a low-refractive layer containing a binder resin and hollowinorganic nanoparticles and solid inorganic nanoparticles which aredispersed in the binder resin, wherein a ratio of an average particlediameter of the solid inorganic nanoparticles to an average particlediameter of the hollow inorganic nanoparticles is 0.15 to 0.55, andwherein at least 70 vol % of the entire solid inorganic nanoparticlesare present within a distance corresponding to 50% of an entirethickness of the low-refractive layer from the interface between thehard coating layer and the low-refractive layer.

The present inventors conducted research into an anti-reflective filmand confirmed through experiments that an anti-reflective film includinga low-refractive layer containing hollow particles and solid particleshaving the specific average particle diameter ratio as described abovemay have a lower reflectance and a high light transmittance andsimultaneously implement high scratch resistance and anti-pollutionproperty, thereby completing the present invention.

In more detail, since the ratio of the average particle diameter of thesolid particles to the average particle diameter of the hollow particlesin the low-refractive layer is 0.55 or less, or 0.15 to 0.55, or 0.26 to0.55, or 0.27 to 0.40, or 0.280 to 0.380, the hollow particles and thesolid particles may be unevenly and differently distributed in thelow-refractive layer. For example, regions of the low-refractive layerin which the hollow particles and the solid particles are mainlydistributed, respectively, may be positioned at different distances froman interface between the hard coating layer and the low-refractivelayer.

As described above, as the regions of the low-refractive layer in whichthe hollow particles and the solid particles are mainly distributed aredifferent from each other, the low-refractive layer may have a uniqueinternal structure and a unique arrangement pattern of components tothereby have a lower reflectance. In addition, as the regions of thelow-refractive layer in which the hollow particles and the solidparticles are mainly distributed are different from each other, surfacecharacteristics of the low-refractive layer are also changed together,thereby making it possible to implement further improved scratchresistance and anti-pollution property.

The concrete contents about the solid inorganic nanoparticles and thehollow inorganic nanoparticles are as described above in theantireflection film of one embodiment of the present invention.

In the case of mainly distributing the solid inorganic nanoparticles ina region of the low-refractive layer of the anti-reflective film closeto the interface between the hard coating layer and the low-refractivelayer and mainly distributing the hollow inorganic nanoparticles in aregion of the low-refractive layer oppose to the interface, it ispossible to achieve a reflectance lower than an actual reflectance whichcould be obtained using the inorganic particles in the past, and thelow-refractive layer may simultaneously implement significantly improvedscratch resistance and anti-pollution property.

Specific distribution of the solid inorganic nanoparticles and thehollow inorganic nanoparticles in the low-refractive layer may beobtained by adjusting the ratio of the average particle diameters of thesolid inorganic nanoparticles and the hollow inorganic nanoparticles andadjusting a drying temperature of a photocurable resin composition forforming a low-refractive layer, containing the two kinds ofnanoparticles as described above in a specific manufacturing method tobe described below.

The low-refractive layer may contain the binder resin and the hollowinorganic nanoparticles and the solid inorganic nanoparticles which aredispersed in the binder resin, and be formed on one surface of the hardcoating layer, wherein at least 70 vol % of the entire solid inorganicnanoparticles may be present within a distance corresponding to 50% ofan entire thickness of the low-refractive layer from the interfacebetween the hard coating layer and the low-refractive layer.

Further, as described above, the hollow inorganic nanoparticles may bemainly distributed in the region of the low-refractive layer opposite tothe interface between the hard coating layer and low-refractive layer.In detail, at least 30 vol % of the entire hollow inorganicnanoparticles may be present at a distance farther than that of theentire solid inorganic nanoparticles from the interface between the hardcoating layer and low-refractive layer in a thickness direction of thelow-refractive layer.

In specific, at least 30 vol %, or 50 vol %, or 70 vol % of the entirehollow inorganic nanoparticles may be present in a region of thelow-refractive layer at a distance exceeding 50% of the entire thicknessof the low-refractive layer from the interface between the hard coatinglayer and the low-refractive layer (a region within a point exceeding50% of the total thickness of the low refraction layer from theinterface between the hard coat layer and the low-refractive layer andthe other surface of the low refraction layer facing the interface).

In more detail, at least 70 vol % of the entire solid inorganicnanoparticles may be present within a distance corresponding to 30% ofthe entire thickness of the low-refractive layer from the interfacebetween the hard coating layer and the low-refractive layer. Inaddition, at least 70 vol % of the entire hollow inorganic nanoparticlesmay be present in a region of the low-refractive layer at a distanceexceeding 30% of the entire thickness of the low-refractive layer fromthe interface between the hard coating layer and the low-refractivelayer.

The hard coating layer contains a binder resin containing a photocurableresin, and organic or inorganic fine particles dispersed in the binderresin.

A particle diameter of the organic or inorganic fine particles is notspecifically limited, but for example, the organic fine particles mayhave a particle diameter of 1 to 10 μm, and the inorganic fine particlesmay have a particle diameter of 1 nm to 500 nm, or 1 nm to 300 nm.

The more specific details to the binder resin and the organic orinorganic fine particles of the hard coat layer include theabove-described contents of the antireflection film of one embodiment ofthe present invention. In addition, more specific details to theanti-reflection film of another embodiment include the above-mentioneddetails to the anti-reflection film of one embodiment of the presentinvention.

Advantageous Effects

According to the present invention, the anti-reflective film capable ofhaving a low reflectance and a high light transmittance, simultaneouslyimplementing high scratch resistance and anti-pollution property, andenhancing sharpness of a screen of a display device, and a manufacturingmethod thereof may be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a transmission electron microscope (TEM) photograph of a crosssection of an anti-reflective film in Example 1.

FIG. 2 is a TEM photograph of a cross section of an anti-reflective filmin Example 2.

FIG. 3 is a TEM photograph of a cross section of an anti-reflective filmin Example 3.

FIG. 4 is a TEM photograph of a cross section of an anti-reflective filmin Example 4.

FIG. 5 is a TEM photograph of a cross section of an anti-reflective filmin Example 5.

FIG. 6 is a TEM photograph of a cross section of an anti-reflective filmin Comparative Example 6.

FIG. 7 is a TEM photograph of a cross section of an anti-reflective filmin Comparative Example 1.

FIG. 8 is a TEM photograph of a cross section of an anti-reflective filmin Comparative Example 2.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present invention will be described in more detail through thefollowing Examples. However, the following Examples are only toexemplify the present invention, and contents of the present inventionare not limited by the following Examples.

Preparation Example Preparation Example: Manufacturing of Hard CoatingFilm

A salt-type antistatic hard coating solution (KYOEISHA Chemical, solidcontent: 50 wt %, product name: LJD-1000) was coated on a triacetylcellulose film using a #10 Mayer bar, dried at 90 degree for 1 minute,and irradiated with UV light (150 mJ/cm²), thereby manufacturing a hardcoating film having a thickness of about 5 to 6 μm.

Examples 1 to 5: Manufacturing of Anti-Reflective Film Example 1 (1)Preparation of Photocurable Coating Composition for FormingLow-Refractive Layer

Based on 100 parts by weight of pentaerythritoltriacrylate (PETA), 281parts by weight of hollow silica nanoparticles (diameter range: about 44nm to 61 nm, manufactured by JSC catalyst and chemicals), 63 parts byweight of solid silica nanoparticles (diameter range: about 12.7 nm to17 nm), 131 parts by weight of a first fluorine-containing compound(X-71-1203M, ShinEtsu), 19 parts by weight of a secondfluorine-containing compound (RS-537, DIC), and 31 parts by weight of aninitiator (Irgacure 127, Ciba) were diluted in a methyl isobutyl ketone(MIBK) solvent so that a solid content was 3 wt %.

(2) Manufacturing of Low-Refractive Layer and Anti-Reflective Film

The photocurable coating composition obtained above was coated on thehard coating film in Preparation Example using a #4 Mayer bar so as tohave a thickness of about 110 to 120 nm, and dried and cured at atemperature illustrated in the following Table 1 for a time illustratedin the following Table 1. At the time of curing, the dried coatingresultant was irradiated with UV light (252 mJ/cm²) under nitrogenpurging.

The longest diameter of 100 to 170 of the hollow silica nanoparticlesand the solid silica nanoparticles contained in the formed lowrefraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 55.9 nm, average diameter of solid type silicananoparticles: 14.5 nm).

Example 2 (1) Preparation of Photocurable Coating Composition forForming Low-Refractive Layer

Based on 100 parts by weight trimethylolpropane triacrylate (TMPTA), 283parts by weight of hollow silica nanoparticles (diameter range: about 42nm to 66 nm, manufactured by JSC catalyst and chemicals), 59 parts byweight of solid silica nanoparticles (diameter range: about 12 nm to 19nm), 115 parts by weight of a first fluorine-containing compound(X-71-1203M, ShinEtsu), 15.5 parts by weight of a secondfluorine-containing compound (RS-537, DIC), and 10 parts by weight of aninitiator (Irgacure 127, Ciba) were diluted in a methyl isobutyl ketone(MIBK) solvent so that a solid content was 3 wt %.

(2) Manufacturing of Low-Refractive Layer and Anti-Reflective Film

The photocurable coating composition obtained above was coated on thehard coating film in Preparation Example using a #4 Mayer bar so as tohave a thickness of about 110 to 120 nm, and dried and cured at atemperature illustrated in the following Table 1 for a time illustratedin the following Table 1. At the time of curing, the dried coatingresultant was irradiated with UV light (252 mJ/cm²) under nitrogenpurging. The longest diameter of 100 to 170 of the hollow silicananoparticles and the solid silica nanoparticles contained in the formedlow refraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 54.9 nm, average diameter of solid type silicananoparticles: 14.5 nm).

Example 3 (1) Preparation of Photocurable Coating Composition forForming Low-Refractive Layer

Based on 100 parts by weight of pentaerythritoltriacrylate (PETA), 281parts by weight of hollow silica nanoparticles (diameter range: about 43nm to 71 nm, manufactured by JSC catalyst and chemicals), 63 parts byweight of solid silica nanoparticles (diameter range: about 13 nm to 16nm), 111 parts by weight of a first fluorine-containing compound(X-71-1203M, ShinEtsu), 30 parts by weight of a secondfluorine-containing compound (RS-537, DIC), and 23 parts by weight of aninitiator (Irgacure 127, Ciba) were diluted in a methyl isobutyl ketone(MIBK) solvent so that a solid content was 3 wt %.

(2) Manufacturing of Low-Refractive Layer and Anti-Reflective Film

The photocurable coating composition obtained above was coated on thehard coating film in Preparation Example using a #4 Mayer bar so as tohave a thickness of about 110 to 120 nm, and dried and cured at atemperature illustrated in the following Table 1 for a time illustratedin the following Table 1. At the time of curing, the dried coatingresultant was irradiated with UV light (252 mJ/cm²) under nitrogenpurging. The longest diameter of 100 to 170 of the hollow silicananoparticles and the solid silica nanoparticles contained in the formedlow refraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 54.5 nm, average diameter of solid type silicananoparticles: 19.5 nm).

Example 4 (1) Preparation of Photocurable Coating Composition forForming Low-Refractive Layer

Based on 100 parts by weight of trimethylolpropane triacrylate (TMPTA),264 parts by weight of hollow silica nanoparticles (diameter range:about 38 nm to 82 nm, manufactured by JSC catalyst and chemicals), 60parts by weight of solid silica nanoparticles (diameter range: about 15nm to 19 nm), 100 parts by weight of a first fluorine-containingcompound (X-71-1203M, ShinEtsu), 50 parts by weight of a secondfluorine-containing compound (RS-537, DIC), and 30 parts by weight of aninitiator (Irgacure 127, Ciba) were diluted in a methyl isobutyl ketone(MIBK) solvent so that a solid content was 3 wt %.

(2) Manufacturing of Low-Refractive Layer and Anti-Reflective Film

The photocurable coating composition obtained above was coated on thehard coating film in Preparation Example using a #4 Mayer bar so as tohave a thickness of about 110 to 120 nm, and dried and cured at atemperature illustrated in the following Table 1 for a time illustratedin the following Table 1. At the time of curing, the dried coatingresultant was irradiated with UV light (252 mJ/cm²) under nitrogenpurging. The longest diameter of 100 to 170 of the hollow silicananoparticles and the solid silica nanoparticles contained in the formedlow refraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 55.4 nm, average diameter of solid type silicananoparticles: 17.1 nm).

Example 5 (1) Preparation of Photocurable Coating Composition forForming Low-Refractive Layer

Based on 100 parts by weight of pentaerythritoltriacrylate (PETA), 414parts by weight of hollow silica nanoparticles (diameter range: about 43nm to 81 nm, manufactured by JSC catalyst and chemicals), 38 parts byweight of solid silica nanoparticles (diameter range: about 14 nm to 19nm), 167 parts by weight of a fluorine-containing compound (RS-537,DIC), 33 parts by weight of an initiator (Irgacure 127, Ciba), and 110parts by weight of 3-methacryloxypropylmethyldimethoxysilane (molecularweight: 234.3) were diluted in a methyl isobutyl ketone (MIBK) solventso that a solid content was 3.2 wt %.

(2) Manufacturing of Low-Refractive Layer and Anti-Reflective Film

The photocurable coating composition obtained above was coated on thehard coating film in Preparation Example using a #4 Mayer bar so as tohave a thickness of about 110 to 120 nm, and dried and cured at atemperature illustrated in the following Table 1 for a time illustratedin the following Table 1. At the time of curing, the dried coatingresultant was irradiated with UV light (252 mJ/cm²) under nitrogenpurging. The longest diameter of 100 to 170 of the hollow silicananoparticles and the solid silica nanoparticles contained in the formedlow refraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 55.5 nm, average diameter of solid type silicananoparticles: 17.1 nm).

Example 6 (1) Preparation Example: Manufacturing of Hard Coating Film(HD2)

30 g of pentaerythritol triacrylate, 2.5 g of high molecular weightcopolymer (BEAMSET 371, Arakawa Co., Epoxy Acrylate, molecular qverageweight 40,000), 20 g of methyl ethyl ketone, and 0.5 g of leveling agent(Tego wet 270) were uniformy mixed. After that, 2 g of anacrylic-styrene copolymer (volume average particle diameter: 2 μm,manufacturer: Sekisui Plastic) as fine particles having a particlediameter of 1.525 was added into the mixure, and a hard coatingcomposition was prepared.

The hard coating composition obtained above was coated on atriacetylcellulose film using a #10 Mayer bar, and dried and cured at90° C. for 1 minute. At the time of curing, the dried coating resultantwas irradiated with UV light (150 mJ/cm²) under nitrogen purging, and ahard coating film having a thickness of 5 mu m was prepared.

(2) Preparation of Photocurable Coating Composition for FormingLow-Refractive Layer

Based on 100 parts by weight of Trimethylolpropane triacrylate (TMPTA),283 parts by weight of hollow silica nanoparticles (diameter range:about 40 nm to 68 nm, manufactured by JSC catalyst and chemicals), 59parts by weight of solid silica nanoparticles (diameter range: about 14nm to 17 nm), 115 parts by weight of a first fluorine compound(X-71-1203M, ShinEtsu), 15.5 parts by weight of a second fluorinecompound (RS-537, manufactured by DIC Corporation), and 10 parts byweight of an initiator (Irgacure 127) were diluted in a methyl isobutylketone (MIBK) solvent so that a solid content was 3.2 wt %.

The photocurable coating composition obtained above was coated on thehard coating film (HD2) using a #4 Mayer bar so as to have a thicknessof about 110 to 120 nm, and dried and cured at a temperature of 60° C.for 1 minute to form a low refractive layer to prepare an antireflectionfilm. At the time of curing, the dried coating resultant was irradiatedwith UV light (252 mJ/cm²) under nitrogen purging. The longest diameterof 100 to 170 of the hollow silica nanoparticles and the solid silicananoparticles contained in the formed low refraction layer were measuredrespectively by using a transmission electron microscope (TEM). Afterrepeating 10 times of the measuring, the average particle diameter ofthe hollow silica nanoparticles and the solid silica nanoparticles weredetermined (average diameter of hollow silica nanoparticles: 55.4 nm,average diameter of solid type silica nanoparticles: 14.7 nm).

TABLE 1 Drying temperature (° C.) Drying Time Example 1 40 1 min Example2 60 1 min Example 3 80 1 min Example 4 60 2 min Example 5 60 1 minExample 6 60 1 min

Comparative Example: Manufacturing of Anti-Reflective Film ComparativeExample 1

An anti-reflective film was manufactured by the same method as inExample 1 except for using solid silica nanoparticles (diameter range:about 34 nm to 80 nm).

The longest diameter of 100 to 170 of the hollow silica nanoparticlesand the solid silica nanoparticles contained in the formed lowrefraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 54.6 nm, average diameter of solid type silicananoparticles: 53.2 nm).

Comparative Example 2

An anti-reflective film was manufactured by the same method as inExample 2 except for using solid silica nanoparticles (diameter range:about 36 nm to 48 nm)

The longest diameter of 100 to 170 of the hollow silica nanoparticlesand the solid silica nanoparticles contained in the formed lowrefraction layer were measured respectively by using a transmissionelectron microscope (TEM). After repeating 10 times of the measuring,the average particle diameter of the hollow silica nanoparticles and thesolid silica nanoparticles were determined (average diameter of hollowsilica nanoparticles: 54.5 nm, average diameter of solid type silicananoparticles: 41.1 nm).

Experimental Example: Measurement of Physical Properties ofAnti-Reflective Film

Experiments composed of the following categories were performed on theanti-reflective films obtained in Examples and Comparative Examples.

1. Measurement of Average Reflectance of Anti-Reflective Film

Average reflectances of the anti-reflective films obtained in Examplesand Comparative Examples in a visible light region (380 to 780 nm) weremeasured using Solidspec 3700 (SHIMADZU).

2. Measurement of Anti-Pollution Property

An anti-pollution property was measured by drawing a straight linehaving a length of 5 cm on surfaces of the anti-reflective filmsobtained in Examples and Comparative Examples using a black name pen andconfirming the number of scrubbing actions required for erasing thestraight line at the time of scrubbing the antireflective film with awiper.

Measurement Standard

◯: The number of rubbing actions required for erasing the straight linewas 10 or less.

Δ: The number of rubbing actions required for erasing the straight linewas 11 to 20.

X: The number of rubbing actions required for erasing the straight linewas more than 20.

3. Measurement of Scratch Resistance

A steel wool was rubbed on surfaces of the anti-reflective filmsobtained in Examples and Comparative Examples while applying a loadthereto and reciprocating the anti-reflective film at a rate of 27 rpm10 times. A maximum load at which the number of scratch (1 cm or less)observed by the naked eyes was 1 or less was measured.

TABLE 2 Average Scratch Anti- reflectance Resistance pollution Phase-(%) (g) Property separation Example1 0.63 500 ◯ ◯ Example2 0.62 500 ◯ ◯Example3 0.67 500 ◯ ◯ Example4 0.64 500 ◯ ◯ Example5 0.63 500 ◯ ◯Example6 0.65 500 ◯ ◯ Comparative 0.80 50 X X Example1 Comparative 0.8250 X X Example2

As illustrated in Table 2, it was confirmed that in the low-refractivelayers of the anti-reflective films in Examples 1 to 6, a ratio of theparticle diameter of the solid particles to the particle diameter of thehollow particles contained therein was 0.55 or less, and thus, theanti-reflective films may have low reflectance of 0.70% or less in thevisible light region, and simultaneously implement high scratchresistance and anti-pollution property.

Further, as illustrated in FIGS. 1 to 6, it was confirmed that in thelow-refractive layers of the anti-reflective films in Examples 1 to 4,phase separation between the hollow inorganic nanoparticles and thesolid inorganic nanoparticles occurred, most of the solid inorganicnanoparticles were present and concentrated toward an interface betweenthe hard coating layer and the low-refractive layer of theanti-reflective film, and most of the hollow inorganic nanoparticleswere present and concentrated in a region far from the hard coatinglayer.

As illustrated in Table 2, it was confirmed that in the low-refractivelayers of the anti-reflective films in Comparative Examples 1 and 2, aratio of the particle diameter of the solid particles to the particlediameter of the hollow particles was more than 0.55, and as illustratedin FIGS. 7 and 8, the hollow inorganic nanoparticles and the solidinorganic nanoparticles were not phase-separated, but mixedly existed.

In addition, as illustrated in Table 2, it was confirmed thatreflectances were relatively high, and low scratch resistance andanti-pollution property were exhibited.

What is claimed is:
 1. An anti-reflective film comprising: a hardcoating layer; and a low refractive layer containing a binder resin andhollow inorganic nanoparticles and solid inorganic nanoparticles whichare dispersed in the binder resin, wherein a ratio of an averageparticle diameter of the solid inorganic nanoparticles to an averageparticle diameter of the hollow inorganic nanoparticles is 0.26 to 0.55,wherein the low-refractive layer includes the hollow inorganicnanoparticles in a higher amount by weight than the solid inorganicnanoparticles, and wherein at least 70 vol % of the entire solidinorganic nanoparticles are present within a distance corresponding to50% of an entire thickness of the low-refractive layer from theinterface between the hard coating layer and the low-refractive layer.2. The anti-reflective film of claim 1, wherein: at least 30 vol % ofthe entire hollow inorganic nanoparticles are present in a region of thelow-refractive layer at a distance exceeding 50% of the entire thicknessof the low-refractive layer from the interface between the hard coatinglayer and the low-refractive layer.
 3. The anti-reflective film of claim1, wherein: the average particle diameter of the hollow particles is ina range of 40 nm to 100 nm, and a particle diameter of the hollowparticles is in a range of 10 nm to 200 nm.
 4. The anti-reflective filmof claim 1, wherein: the average particle diameter of the solidparticles is in a range of 1 nm to 30 nm, and a particle diameter of thesolid particles is in a range of 0.1 nm to 100 nm.
 5. Theanti-reflective film of claim 1, wherein: the solid inorganicnanoparticles are further distributed in a region close to an interfacebetween the hard coating layer and the low-refractive layer than thehollow inorganic nanoparticles.
 6. The anti-reflective film of claim 1,wherein: at least 70 vol % of the entire solid inorganic nanoparticlesare present within a distance corresponding to 50% of an entirethickness of the low-refractive layer from an interface between the hardcoating layer and the low-refractive layer.
 7. The anti-reflective filmof claim 1, wherein: at least 30 vol % of the entire hollow inorganicnanoparticles are present at a distance farther than that of the entiresolid inorganic nanoparticles from an interface between the hard coatinglayer and low-refractive layer in a thickness direction of thelow-refractive layer.
 8. The anti-reflective film of claim 1, wherein:at least 70 vol % of the entire solid inorganic nanoparticles arepresent within a distance corresponding to 30% of an entire thickness ofthe low-refractive layer from an interface between the hard coatinglayer and the low-refractive layer.
 9. The anti-reflective film of claim8, wherein: at least 70 vol % of the entire hollow inorganicnanoparticles are present at a distance exceeding 30% of an entirethickness of the low-refractive layer from an interface between the hardcoating layer and the low-refractive layer.
 10. The anti-reflective filmof claim 1, wherein: the low-refractive layer includes a first layercontaining at least 70 vol % of the entire solid inorganic nanoparticlesand a second layer containing at least 70 vol % of the entire hollowinorganic nanoparticles, the first layer being positioned to be closerto an interface between the hard coating layer and the low-refractivelayer than the second layer.
 11. The anti-reflective film of claim 1,wherein: each of the solid inorganic nanoparticles and the hollowinorganic nanoparticles contains one or more reactive functional groupsselected from the group consisting of a hydroxyl group, a (meth)acrylategroup, an epoxide group, a vinyl group, and a thiol group on a surfacethereof.
 12. The anti-reflective film of claim 1, wherein: the binderresin contained in the low-refractive layer contains a cross-linked(co)polymer between a (co)polymer of a photopolymerizable compound and afluorine-containing compound including a photoreactive functional group.13. The anti-reflective film of claim 12, wherein: the low-refractivelayer contains 10 to 400 parts by weight of the hollow inorganicnanoparticles and 10 to 400 parts by weight of the solid inorganicnanoparticles, based on 100 parts by weight of the (co)polymer of thephotopolymerizable compound.
 14. The anti-reflective film of claim 1,wherein: the low-refractive layer further contains a silane basedcompound including one or more reactive functional groups selected fromthe group consisting of a vinyl group and a (meth)acrylate group. 15.The anti-reflective film of claim 14, wherein: the silane based compoundincluding one or more reactive functional groups selected from the groupconsisting of the vinyl group and the (meth)acrylate group has a weightaverage molecular weight of 100 to 5,000.
 16. The anti-reflective filmof claim 14, wherein the silane based compound contains 100 to 1000g/mol equivalent weight of the reactive functional group.
 17. Theanti-reflective film according to claim 1, wherein the hard coatinglayer contains a binder resin containing a photocurable resin, andorganic or inorganic fine particles dispersed in the binder resin. 18.The anti-reflective film according to claim 1, wherein the hard coatinglayer contains a binder resin containing a photocurable resin, andorganic fine particles having a particle diameter of 1 to 10 μm orinorganic fine particles having a particle diameter of 1 nm to 500 nm.19. The anti-reflective film according to claim 1, wherein the film hasa reflectance of 0.70% or less in a wavelength region from 380 nm to 780nm.
 20. An anti-reflective film comprising: a hard coating layercontaining a binder resin containing a photocurable resin, and organicor inorganic fine particles dispersed in the binder resin; and alow-refractive layer containing a binder resin and hollow inorganicnanoparticles and solid inorganic nanoparticles which are dispersed inthe binder resin, wherein a ratio of an average particle diameter of thesolid inorganic nanoparticles to an average particle diameter of thehollow inorganic nanoparticles is 0.15 to 0.55, wherein thelow-refractive layer includes the hollow inorganic nanoparticles in ahigher amount by weight than the solid inorganic nanoparticles, andwherein at least 70 vol % of the entire solid inorganic nanoparticlesare present within a distance corresponding to 50% of an entirethickness of the low-refractive layer from the interface between thehard coating layer and the low-refractive layer.
 21. The anti-reflectivefilm according to claim 20, wherein at least 30 vol % of the entirehollow inorganic nanoparticles are present at a distance exceeding 50%of an entire thickness of the low-refractive layer from an interfacebetween the hard coating layer and the low-refractive layer.
 22. Theanti-reflective film according to claim 20, wherein the organic fineparticles have a particle diameter of 1 to 10 μm, and the inorganic fineparticles have a particle diameter of 1 nm to 500 nm.
 23. Theanti-reflective film according to claim 20, wherein the film has areflectance of 0.70% or less in a wavelength region from 380 nm to 780nm.
 24. The anti-reflective film of claim 20, wherein: thelow-refractive layer further contains a silane based compound includingone or more reactive functional groups selected from the groupconsisting of a vinyl group and a (meth)acrylate group.
 25. Theanti-reflective film of claim 24, wherein the silane based compoundcontains 100 to 1000 g/mol equivalent weight of the reactive functionalgroup.